Carbon-based metal-free electrocatalysts: from oxygen reduction to multifunctional electrocatalysis

Since the discovery of N-doped carbon nanotubes as the first carbon-based metal-free electrocatalyst (C-MFEC) for oxygen reduction reaction (ORR) in 2009, C-MFECs have shown multifunctional electrocatalytic activities for many reactions beyond ORR, such as oxygen evolution reaction (OER), hydrogen evolution reaction (HER), carbon dioxide reduction reaction (CO₂RR), nitrogen reduction reaction (NRR), and hydrogen peroxide production reaction (H₂O₂PR). Consequently, C-MFECs have attracted a great deal of interest for various applications, including metal-air batteries, water splitting devices, regenerative fuel cells, solar cells, fuel and chemical production, water purification, to mention a few. By altering the electronic configuration and/or modulating their spin angular momentum, both heteroatom(s) doping and structural defects (e.g., atomic vacancy, edge) have been demonstrated to create catalytic active sites in the skeleton of graphitic carbon materials. Although certain C-MFECs have been made to be comparable to or even better than their counterparts based on noble metals, transition metals and/or their hybrids, further research and development are necessary in order to translate C-MFECs for practical applications. In this article, we present a timely and comprehensive, but critical, review on recent advancements in the field of C-MFECs within the past five years or so by discussing various types of electrocatalytic reactions catalyzed by C-MFECs. An emphasis is given to potential applications of C-MFECs for energy conversion and storage. The structure-property relationship for and mechanistic understanding of C-MFECs will also be discussed, along with the current challenges and future perspectives.